WO2002064713A1 - Lubrifiants concentres a base d'alcool - Google Patents

Lubrifiants concentres a base d'alcool Download PDF

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Publication number
WO2002064713A1
WO2002064713A1 PCT/EP2002/001193 EP0201193W WO02064713A1 WO 2002064713 A1 WO2002064713 A1 WO 2002064713A1 EP 0201193 W EP0201193 W EP 0201193W WO 02064713 A1 WO02064713 A1 WO 02064713A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricant
lubricant concentrate
concentrate according
molecule
transport chains
Prior art date
Application number
PCT/EP2002/001193
Other languages
German (de)
English (en)
Inventor
Stefan Küpper
Michael Schneider
Original Assignee
Ecolab Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecolab Inc filed Critical Ecolab Inc
Priority to BRPI0207282-3A priority Critical patent/BR0207282B1/pt
Priority to EP02716728A priority patent/EP1360267B1/fr
Priority to PL02362386A priority patent/PL362386A1/xx
Priority to US10/467,702 priority patent/US7462584B2/en
Priority to CA2443807A priority patent/CA2443807C/fr
Priority to JP2002565031A priority patent/JP2004521978A/ja
Priority to DE50208132T priority patent/DE50208132D1/de
Publication of WO2002064713A1 publication Critical patent/WO2002064713A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C10M173/025Lubricating compositions containing more than 10% water not containing mineral or fatty oils for lubricating conveyor belts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils

Definitions

  • the present invention relates to lubricant concentrates based on selected alcohols in combination with at least one selected nitrogen compound and / or a selected organic carboxylic acid.
  • the present invention also encompasses the use of these lubricant concentrates, methods and a system in which these lubricant concentrates are a component.
  • the containers to be filled in the filling plants are transported by means of conveyors of various designs and materials, for example by means of plate conveyor belts or chain-like arrangements, which are generally referred to below as transport chains.
  • the transporters establish the connection between the various optional treatment stages of the filling process such as B. unpacker, bottle washer, filler, capper, labeler, packer, etc.
  • the containers can be of various shapes, in particular glass and plastic bottles, cans, glasses, barrels, beverage containers (KEG), paper and cardboard containers.
  • KEG beverage containers
  • the transport chains must be lubricated in a suitable manner so that excessive friction against the containers is avoided.
  • Diluted aqueous solutions containing suitable anti-friction agents are usually used for lubrication.
  • the transport chains are brought into contact with the aqueous solutions, for example by immersion or spraying, in which case one speaks of splash lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
  • the chain lubricants previously used as lubricants are mostly based on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts.
  • Soap-based lubricant preparations continue to be dependent on water temperature. 10. Soap-based lubricants only have a low storage stability, especially at low temperatures.
  • the EDTA ethylenediaminetetraacetate contained in many products is known to be poorly biodegradable.
  • Such soap-based lubricant preparations are not suitable for all transport goods made of plastic, since in many cases stress corrosion cracking on the transport goods occurs when these agents are used.
  • DE-A-36 31 953 describes a method for lubricating chain-shaped bottle conveyor belts in beverage filling companies, in particular in breweries, and for cleaning the belts using a liquid cleaning agent, which is characterized in that the chain-shaped bottle conveyor belts are based on belt lubricants neutralized primary fatty amines, which preferably have 12 to 18 carbon atoms and contain an unsaturated fraction of more than 10%.
  • R1 is a saturated or unsaturated, branched or linear alkyl group with 8 to 22 C atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms or - A-NH 2 ;
  • A is a linear or branched alkylene group with 1 to 8 carbon atoms; and A ⁇ is a linear or branched alkylene group having 2 to 4 carbon atoms.
  • DE-A-39 05 548 discloses lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
  • R is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) or - (CH 2 CH 2 CH 2 O) r can be substituted,
  • R 1 represents hydrogen, an alkyl radical having 1 to 4 carbon atoms, a hydroxyalkyl radical having 1 to 4 carbon atoms or a radical -R 3 COOM
  • R 2 only in the case that M represents a negative charge for hydrogen, an alkyl radical with 1 to 4 C atoms, or a hydroxyalkyl radical with 1 to 4 C atoms,
  • R3 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 carbon atoms, which may be replaced by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) or - (CH 2 CH 2 CH 2 O) r can be substituted,
  • R 4 represents a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, which may have at least one amine, imine, hydroxyl, halogen and / or carboxy radical as substituent, a substituted or unsubstituted phenyl radical which may have at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical with 6 to 22 C atoms as substituents,
  • R for hydrogen or - independently of R 4 - for a radical R 4 ,
  • X stands for an anion from the group amidosulfonate, nitrate, halide, sulfate, hydrogen carbonate, carbonate, phosphate or R ⁇ -COO " ,
  • for hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 carbon atoms or alkenyl radical having 2 to 20 carbon atoms, which may have at least one hydroxyl, amine or imine radical as a substituent, or one substituted or unsubstituted Phe- nyl radical, which may have an alkyl radical with 1 to 20 C atoms as a substituent, and
  • R 7 and R 8 each independently of one another represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have at least one hydroxyl, amine or imine radical as substituents, or a substituted or unsubstituted phenyl radical, which may have an alkyl radical with 1 to 20 C atoms as substituents,
  • M for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 carbon atoms, a benzyl radical or a negative charge
  • n for an integer in the range from 1 to 12
  • m for an integer in the range from 0 to 5 and
  • I stands for a number in the range from 0 to 5, containing alkyldimethylamine oxides and / or alkyl oligoglycosides as nonionic
  • EP-B-629 234 discloses a lubricant combination consisting of a) one or more compounds of the formula
  • R 1 represents a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, which may optionally be substituted by -OH, -NH 2 , -NH-, -CO-, halogen or a carboxyl radical
  • R 2 represents a carboxyl radical with 2 to 7 C atoms
  • M for hydrogen, alkali metal, ammonium, an alkyl radical with 1 to 4 C-
  • Atoms or a benzyl radical and n is an integer in the range from 1 to 6, b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or mono- or polyunsaturated carboxylic acids having 2 to 22 carbon atoms, c) optionally water and Additives and / or auxiliaries.
  • WO 94/03562 describes a lubricant concentrate based on fatty amines and, if appropriate, customary diluents or auxiliaries or additives, characterized in that it contains at least one polyamine derivative of a fatty amine and / or a salt of such an amine, the proportion of said polyamine derivatives of Fatty amines in the total formulation is 1 to 100% by weight.
  • this lubricant concentrate contains at least one polyamine derivative of a fatty amine of the general formula
  • R is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, the substituents being selected from amino, imino, hydroxy, halogen and carboxy, or a substituted or unsubstituted phenyl radical, where the Substituents are selected from amino, imino, hydroxyl, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms;
  • Lubricants based on polytetrafluoroethylene are used in some filling plants. These are in the form of dispersions and are not applied to the chains via nozzles, as is usually the practice, but with brushes. These agents have the advantage that they bring about a substantial reduction in the friction between the conveyor belts and the goods to be transported. In addition, the polytetrafluoroethylene adheres very strongly to the chains. In practice, it turned out to be disadvantageous that the overall hygienic condition with regard to contamination and contamination of the transport chains deteriorated. This even went so far that the performance profile of the lubricant deteriorated over time due to the increase in contamination.
  • the commonly used lubricants have the disadvantage that they form a firmly adhering film on the transport chains, which is not easy to remove by simply rinsing with water. Residues and abrasives can accumulate in this film and lead to hygiene and operational problems in the company.
  • the unpublished application DE 199 42 535.3 provides lubricants based on polyhydroxy compounds which are hydrophilic due to their molecular structure and at the same time improve the lubricating performance compared to the amines usually used as lubricants.
  • Polyhydroxy compounds selected from alkanediols or alkanetriols, very particularly preferably glycerol, or their polymers and their esters and ethers are mentioned as particularly preferred.
  • the present invention thus relates to a lubricant concentrate containing at least one non-nitrogenous alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds and their esters and ethers, and additionally at least one further component selected from a) nitrogenous, organic, preferably aliphatic compounds with less than 14 carbon atoms in the molecule and less than 8 directly connected carbon atoms in the molecule and / or b) an organic acid with 1 to 18, preferably 1 to 10 carbon atoms in the molecule or salts thereof.
  • non-nitrogenous alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds and their esters and ethers
  • at least one further component selected from a) nitrogenous, organic, preferably aliphatic compounds with less than 14 carbon atoms in the molecule and less than 8 directly connected carbon atoms in the molecule and / or b) an organic acid with 1 to 18, preferably 1 to 10 carbon atoms in the molecule or salts thereof.
  • the proportion of the alcoholic component, based on the total concentrate is greater than 20% by weight, particularly preferably greater than 25% by weight and very particularly preferably greater than 50% by weight and in particular greater than 70% by weight.
  • the lubricant concentrate according to the invention preferably contains at least glycerol as the alcoholic component.
  • the nitrogen-containing compound a) has fewer than 7 carbon atoms in the molecule.
  • the nitrogen-containing compound a) present in the lubricant concentrate according to the invention preferably contains additional OH groups in the molecule, with a compound of the formula I being particularly preferred as the nitrogen-containing compound a)
  • monoethanolamine and / or triethanolamine are present as nitrogen-containing compound a).
  • the proportion of nitrogen-containing compound a), based on the total concentrate is 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight.
  • the lubricant concentrate according to the invention contains 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight, of the organic carboxylic acid b).
  • the preferred organic carboxylic acid b) contains acetic acid and / or caproic acid in the lubricant concentrate according to the invention.
  • the lubricant concentrate according to the invention is preferably in the form of a liquid, solution, gel, emulsion, paste or dispersion.
  • At least one antimicrobial component additionally selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, Oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl- butyl carbamate, iodine, iodophores, peroxides, peracids is contained.
  • the lubricant concentrates of the present invention can additionally also contain components selected from fluorine and silicone compounds, the fluorine compound preferably being selected from the groups of per- or partially fluorinated monomeric organic compounds, pure and mixed di- and oligomers which based on at least one per- or partially fluorinated organic monomer, pure and mixed polymers based on at least one per- or partially fluorinated organic monomer.
  • fluorine and silicone compounds the fluorine compound preferably being selected from the groups of per- or partially fluorinated monomeric organic compounds, pure and mixed di- and oligomers which based on at least one per- or partially fluorinated organic monomer, pure and mixed polymers based on at least one per- or partially fluorinated organic monomer.
  • the silicone compounds are preferably selected from the group of polysiloxanes and particularly preferably from the groups of linear, branched, cyclic and crosslinked polysiloxanes.
  • the lubricant concentrates according to the invention can contain further components selected from the groups of surfactants and solubilizers, it being particularly preferred that at least one alkyl polyglycoside is contained as the surfactant.
  • Further constituents can be fatty alkyl amines with more than 10 C atoms and / or their alkoxylates, in particular coconut fatty amine ethoxylates and / or imidazoline compounds and / or amphoteric surfactants and / or nonionic surfactants and / or ether carboxylic acids and / or ether amine compounds with more than 10 C atoms.
  • Another object of the present invention is the use of a lubricant concentrate according to the invention or a dilute solution of a lubricant concentrate according to the invention for the transport of plastic, cardboard, metal or glass containers, primarily in the food processing industry, the plastic containers to be transported is preferably those which contain at least one polymer selected from the groups of polyethylene terephthalate (PET), polyethylene naphtenate (PEN), polycarbonate (PC), PVC and are very particularly preferably PET beverage bottles.
  • PET polyethylene terephthalate
  • PEN polyethylene naphtenate
  • PC polycarbonate
  • PVC polycarbonate
  • additional antimicrobial active ingredients which are particularly preferably selected from organic peracids, chlorine dioxide or ozone, are added separately during use.
  • the lubricant concentrates are applied to the conveyor belts using an auxiliary agent which is selected, for example, from a brush, sponge, roller, cloth, rag, brush, wiper, rubber, spraying device , the lubricant concentrate preferably being used in undiluted form, that is to say with a dilution factor of 0 or diluted form with a dilution factor of up to less than 10,000.
  • auxiliary agent which is selected, for example, from a brush, sponge, roller, cloth, rag, brush, wiper, rubber, spraying device , the lubricant concentrate preferably being used in undiluted form, that is to say with a dilution factor of 0 or diluted form with a dilution factor of up to less than 10,000.
  • Particularly preferred dilution factors are between 0 to 10 and very particularly preferably between 0 and 2.
  • Another object of the present invention is a method for maintaining the smooth running of transport chains by the computer-controlled application of a lubricant concentrate according to the invention, which is preferably diluted before application, at predetermined positions of the transport chains and by periodic application of chain cleaning agent and / or rinse or rinse water ,
  • the present invention also relates to a system for maintaining the smooth running of transport chains, comprising a lubricant concentrate according to the invention and a system for lubricating and cleaning transport chains and a chain cleaning agent, with at least one tank for holding the lubricant in the system for lubricating and cleaning transport chains associated feed pump and feed line to the lubricant application element (s) and a tank for receiving the chain cleaning agent with associated feed pump and feed line to the detergent application element (s) as well as a control device controlling the respective application cycles and the respective feed quantities.
  • the lubricant application element and the cleaning agent application element are arranged as a functional unit on a common nozzle holder.
  • the lubricant application element is designed as a compressed air-assisted two-component nozzle.
  • the lubricating effect can be determined by determining the coefficient of friction.
  • the coefficient of friction between the beverage bottle and transport chains is defined as the ratio of the pulling weight which is exerted, for example, on a spring balance when an attempt is made to hold a beverage bottle while the transport chains are running, to the weight of the bottle.
  • the transport chains in the present experiment were made of stainless steel.
  • agents B1, B2 and B3 are sufficiently microbiologically stable so that the addition of preservatives is possible, but is not absolutely necessary for preservation purposes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Belt Conveyors (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne des lubrifiants concentrés contenant au moins un constituant alcoolisé exempt d'azote, sélectionné parmi des composés monohydroxy, dihydroxy et trihydroxy, ainsi que leurs esters et éthers et en outre au moins un autre constituant sélectionné parmi a) des composés organiques, à base d'azote, de préférence aliphatiques, contenant moins de 14 atomes de C dans la molécule et moins de 8 atomes de C reliés directement mutuellement dans la molécule et/ou b) un acide organique ayant entre 1 et 18 atomes de C, de préférence entre 1 et 10 atomes de C dans la molécule.
PCT/EP2002/001193 2001-02-15 2002-02-06 Lubrifiants concentres a base d'alcool WO2002064713A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BRPI0207282-3A BR0207282B1 (pt) 2001-02-15 2002-02-06 concentrado de lubrificante para correia transportadora de gÊneros alimentÍcios e processo para lubrificaÇço de uma correia transportadora para o transporte de contÊineres de bebida.
EP02716728A EP1360267B1 (fr) 2001-02-15 2002-02-06 Lubrifiants concentres a base de glycerol
PL02362386A PL362386A1 (en) 2001-02-15 2002-02-06 Lubricant concentrate based on alcohols
US10/467,702 US7462584B2 (en) 2001-02-15 2002-02-06 Lubricant concentrate based on alcohols
CA2443807A CA2443807C (fr) 2001-02-15 2002-02-06 Concentres de lubrification a base de glycerine
JP2002565031A JP2004521978A (ja) 2001-02-15 2002-02-06 アルコールに基づく潤滑剤濃厚物
DE50208132T DE50208132D1 (de) 2001-02-15 2002-02-06 Schmiermittelkonzentrate auf basis von glycerin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10106954A DE10106954A1 (de) 2001-02-15 2001-02-15 Schmiermittelkonzentrate auf alkoholischer Basis
DE10106954.5 2001-02-15

Publications (1)

Publication Number Publication Date
WO2002064713A1 true WO2002064713A1 (fr) 2002-08-22

Family

ID=7674083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/001193 WO2002064713A1 (fr) 2001-02-15 2002-02-06 Lubrifiants concentres a base d'alcool

Country Status (9)

Country Link
US (1) US7462584B2 (fr)
EP (1) EP1360267B1 (fr)
JP (1) JP2004521978A (fr)
AT (1) ATE339491T1 (fr)
BR (1) BR0207282B1 (fr)
CA (1) CA2443807C (fr)
DE (2) DE10106954A1 (fr)
PL (1) PL362386A1 (fr)
WO (1) WO2002064713A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT16017U1 (de) * 2017-10-05 2018-11-15 Dipl Ing Dr Johann Kellersperg Ölfreies Kühl-Schmiermittel

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7745381B2 (en) 2005-03-15 2010-06-29 Ecolab Inc. Lubricant for conveying containers
US7741257B2 (en) 2005-03-15 2010-06-22 Ecolab Inc. Dry lubricant for conveying containers
JP2008106253A (ja) * 2006-09-29 2008-05-08 Daisan Kogyo Kk コンベア用潤滑剤
CN103119143A (zh) 2010-09-24 2013-05-22 艺康美国股份有限公司 包括乳液的输送机润滑剂和使用它们的方法
DE102011000276A1 (de) * 2011-01-21 2012-07-26 Krones Aktiengesellschaft Vorrichtung und Verfahren zum Bestimmen der Reibung zwischen Kunststoffhohlkörpern aus gleicher Materialzusammensetzung
EP2969864B1 (fr) 2013-03-11 2024-04-24 Ecolab USA Inc. Lubrification de plaques de transfert utilisant une huile ou des émulsions d'huile dans l'eau
US10696915B2 (en) 2015-07-27 2020-06-30 Ecolab Usa Inc. Dry lubricator for plastic and stainless steel surfaces

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EP0538916A1 (fr) * 1988-12-05 1993-04-28 Unilever N.V. Solutions lubrifiantes aqueuses à base d'amines grasses alkylées
US5244589A (en) * 1991-01-16 1993-09-14 Ecolab Inc. Antimicrobial lubricant compositions including a fatty acid and a quaternary
WO1994019438A1 (fr) * 1993-02-19 1994-09-01 Ecolab Inc. Lubrifiant pour bandes transporteuses compatible avec les thermoplastiques
WO2001007545A1 (fr) * 1999-07-21 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Composition de lubrifiant contenant du soufre elementaire pour l'usinage de metaux

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US5255589A (en) * 1992-01-06 1993-10-26 Caulkins Kenneth B Calliope pipe converter, assembly, and method
DE4206506A1 (de) 1992-03-02 1993-09-09 Henkel Kgaa Tensidbasis fuer seifenfreie schmiermittel
KR950702616A (ko) 1992-08-03 1995-07-29 한스 크리스토프 빌크, 게오르그 챠이트 지방족 아민을 기재로 하는 농축 윤활제 및 윤활제 수용액, 그 의 제조방법 및 그의 용도(concentrated lubricant and aqueous lubricant solution based on fatty amines, process for producing them and their use)
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US4434066A (en) * 1980-12-30 1984-02-28 Union Carbide Corporation Water-based energy transmitting fluid compositions
DE3631953A1 (de) * 1986-09-19 1988-03-31 Akzo Gmbh Verfahren zum schmieren und reinigen von flaschentransportbaendern in der getraenkeindustrie
EP0538916A1 (fr) * 1988-12-05 1993-04-28 Unilever N.V. Solutions lubrifiantes aqueuses à base d'amines grasses alkylées
US5244589A (en) * 1991-01-16 1993-09-14 Ecolab Inc. Antimicrobial lubricant compositions including a fatty acid and a quaternary
WO1994019438A1 (fr) * 1993-02-19 1994-09-01 Ecolab Inc. Lubrifiant pour bandes transporteuses compatible avec les thermoplastiques
WO2001007545A1 (fr) * 1999-07-21 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Composition de lubrifiant contenant du soufre elementaire pour l'usinage de metaux

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT16017U1 (de) * 2017-10-05 2018-11-15 Dipl Ing Dr Johann Kellersperg Ölfreies Kühl-Schmiermittel

Also Published As

Publication number Publication date
PL362386A1 (en) 2004-11-02
CA2443807C (fr) 2010-05-25
ATE339491T1 (de) 2006-10-15
US7462584B2 (en) 2008-12-09
US20040097383A1 (en) 2004-05-20
CA2443807A1 (fr) 2002-08-22
BR0207282B1 (pt) 2012-06-12
EP1360267B1 (fr) 2006-09-13
DE50208132D1 (de) 2006-10-26
JP2004521978A (ja) 2004-07-22
EP1360267A1 (fr) 2003-11-12
BR0207282A (pt) 2004-02-10
DE10106954A1 (de) 2002-09-05

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